Degrees of freedom effect on fragmentation in tandem mass spectrometry of singly charged supramolecular aggregates of sodium sulfonates

Authors

  • Serena Indelicato,

    1. Dipartimento di Scienze e Tecnologie Biologiche Chimiche e Farmaceutiche (STEBICEF), Università degli Studi di Palermo, Palermo, Italy
    2. Centro Grandi Apparecchiature - UniNetLab, Università degli Studi di Palermo, Palermo, Italy
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  • David Bongiorno,

    Corresponding author
    1. Dipartimento di Scienze e Tecnologie Biologiche Chimiche e Farmaceutiche (STEBICEF), Università degli Studi di Palermo, Palermo, Italy
    • Centro Grandi Apparecchiature - UniNetLab, Università degli Studi di Palermo, Palermo, Italy
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  • Sergio Indelicato,

    1. CQRC Laboratory, A.O.U.P. ‘P. Giaccone’, Palermo, Italy
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  • Laszlo Drahos,

    1. Institute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Pusztaszeri ut 59–67, Budapest, Hungary
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  • Vincenzo Turco Liveri,

    1. Dipartimento di Scienze e Tecnologie Biologiche Chimiche e Farmaceutiche (STEBICEF), Università degli Studi di Palermo, Palermo, Italy
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  • Lilla Turiák,

    1. Institute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Pusztaszeri ut 59–67, Budapest, Hungary
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  • Karoly Vékey,

    1. Institute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Pusztaszeri ut 59–67, Budapest, Hungary
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  • Leopoldo Ceraulo

    1. Dipartimento di Scienze e Tecnologie Biologiche Chimiche e Farmaceutiche (STEBICEF), Università degli Studi di Palermo, Palermo, Italy
    2. Centro Grandi Apparecchiature - UniNetLab, Università degli Studi di Palermo, Palermo, Italy
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Correspondence to: David Bongiorno, Dipartimento di Chimica e Tecnologie Farmaceutiche, Università di Palermo, Italy. E-mail: dbongiorno@unipa.it

Abstract

The characteristic collision energy (CCE) to obtain 50% fragmentation of positively and negatively single charged noncovalent clusters has been measured. CCE was found to increase linearly with the degrees of freedom (DoF) of the precursor ion, analogously to that observed for synthetic polymers. This suggests that fragmentation behavior (e.g. energy randomization) in covalent molecules and clusters are similar. Analysis of the slope of CCE with molecular size (DoF) indicates that activation energy of fragmentation of these clusters (loss of a monomer unit) is similar to that of the lowest energy fragmentation of protonated leucine–enkephalin. Positively and negatively charged aggregates behave similarly, but the slope of the CCE versus DoF plot is steeper for positive ions, suggesting that these are more stable than their negative counterparts. Copyright © 2013 John Wiley & Sons, Ltd.

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